Process for vinyl chloride manufacture from ethane and ethylene with partial CHl recovery from reactor effluent

ABSTRACT

A process for producing vinyl chloride monomer from ethylene and ethane having input of significant quantities of both ethane and ethylene in input streams to the affiliated reactor where hydrogen chloride in the reactor effluent is only partially recovered from the reactor effluent in the first unit operation after the ethane/ethylene-to-vinyl reaction step or stage. Steps are presented of oxydehydro-chlorination catalytic reaction of ethane, ethylene, hydrogen chloride, oxygen, and chlorine; cooling and condensing the reactor effluent stream; and separating the condensed raw product stream into vinyl chloride monomer and a reactor recycle stream.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 of International Patent Application SerialNumber PCT/US00/27701, filed Oct. 6, 2000, which claims the benefit ofUS provisional application serial number 60/166,897, filed Nov. 22,1999. This application also claims the benefit of International PatentApplication serial number PCT/US00/27272, filed Oct. 3, 2000.

This invention is directed to an apparatus and process for producingvinyl chloride monomer (VCM) from ethane and ethylene. Especially, thisinvention is directed to processes for producing vinyl chloride monomerwhere (1) significant quantities of both ethane and ethylene are presentin input streams to the affiliated reactor, (2) hydrogen chloride in thereactor effluent is only partially recovered from the effluent in thefirst unit operation after the ethane/ethylene-to-vinyl reaction step orstage, and (3) a portion of the remainder of the hydrogen chloride isrecycled in a recycle gas stream to the reactor.

Vinyl chloride is a key material in modern commerce, and most processesdeployed today derive vinyl chloride from 1,2-dichloroethane (EDC) wherethe EDC is first-derived from ethylene; so, from an abstracted referenceframe, at least a three-operation overall system is used (ethylene fromprimary hydrocarbons, preponderantly via thermal cracking; ethylene toEDC; and then EDC to vinyl chloride). There is an inherent long-feltneed in the industry to move toward an approach where vinyl chloride isderived more directly and economically from primary hydrocarbons withouta need to first manufacture and purify ethylene, and the inherenteconomic benefit related to this vision has inspired a significantamount of development.

As a first general area of development, ethane-to-vinyl manufacture isof interest to a number of firms engaged in vinyl chloride production,and a significant amount of literature on the subject is now available.The following paragraphs overview key work related to the embodimentspresented in the new developments of the present disclosure.

GB Patent 1,039,369 entitled “CATALYTIC CONVERSION OF ETHANE TO VINYLCHLORIDE” which issued on Aug. 17, 1966 describes use of multivalentmetals, including those in the lanthanum series, in the production ofvinyl chloride from ethane. The patent describes use of certaincatalysts provided that “steam, available chlorine and oxygen are usedin specific controlled ratios.” The described system operates at atemperature of between 500 and 750° C. Available chlorine in thedescribed technology optionally includes 1,2-dichloroethane.

GB Patent 1,492,945 entitled “PROCESS FOR PRODUCING VINYL CHLORIDE”which issued on Nov. 23, 1977 to John Lynn Barclay discloses a processfor the production of vinyl chloride using lanthanum in a copper-basedethane-to-vinyl catalyst. The authors describe that the lanthanum ispresent to favorably alter the volatility of copper at the elevatedtemperature required for operation. Examples show the advantage ofexcess hydrogen chloride in the affiliated reaction.

GB Patent 2,095,242 entitled “PREPARATION OF MONOCHLORO-OLEFINS BYOXYCHLORINATION OF ALKANES” which issued on Sep. 29, 1982 to David RogerPyke and Robert Reid describes a “process for the production ofmonochlorinated olefins which comprises bringing into reaction atelevated temperature a gaseous mixture comprising an alkane, a source ofchlorine and molecular oxygen in the presence of a . . . catalystcomprising metallic silver and/or a compound thereof and one or morecompounds of manganese, cobalt or nickel”. The authors indicate thatmixtures of ethane and ethylene can be fed to the catalyst. No examplesare given and the specific advantages of ethane/ethylene mixtures arenot disclosed.

GB Patent 2,101,596 entitled “OXYCHLORINATION OF ALKANES TOMONOCHLORINATED OLEFINS” which issued on Jan. 19, 1983 to Robert Reidand David Pyke describes a “process for the production ofmonochlorinated olefins which comprises bringing into reaction atelevated temperature a gaseous mixture comprising an alkane, a source ofchlorine and molecular oxygen in the presence of a . . . catalystcomprising compounds of copper, manganese and titanium and is useful inthe production of vinyl chloride from ethane.” The authors furtherdescribe that “the products of reaction are, in one embodiment, isolatedand used as such or are, in one embodiment, recycled . . . to thereactor . . . to increase the yield of monochlorinated olefin.” Theauthors indicate that mixtures of ethane and ethylene can be fed to thecatalyst. No examples are given and the specific advantages ofethane/ethylene mixtures are not disclosed.

U.S. Pat. No. 3,629,354 entitled “HALOGENATED HYDROCARBONS” which issuedon Dec. 21, 1971 to William Q. Beard, Jr. describes a process for theproduction of vinyl chloride and the co-production of ethylene fromethane in the presence of hydrogen chloride and oxygen. Preferredcatalysts are supported copper or iron. An example in this patent showsexcess hydrogen chloride (HCl) relative to ethane in the reaction. Aratio of one ethane to four hydrogen chlorides is used to produce astream containing 38.4 percent ethylene (which requires no HCl toproduce) and 27.9 percent vinyl chloride (which requires only one moleof HCl per mole of vinyl chloride to produce).

U.S. Pat. No. 3,658,933 entitled “ETHYLENE FROM ETHANE, HALOGEN ANDHYDROGEN HALIDE THROUGH FLUIDIZED CATALYST” which issued on Apr. 25,1972 to William Q. Beard, Jr. describes a process for production ofvinyl halides in a three reactor system combining an oxydehydrogenationreactor, an oxyhalogenation reactor and a dehydrohalogenation reactor.The authors show that (oxy)halodehydrogenation of ethane is, in somecases, enhanced by addition of both halogen and hydrogen halide. As inU.S. Pat. No. 3,629,354, the ethylene generated produces VCM throughconventional oxyhalogenation (oxychlorination) and cracking. HClproduced in the cracking operation is returned to thehalodehydrogenation reactor.

U.S. Pat. No. 3,658,934 entitled “ETHYLENE FROM ETHANE AND HALOGENTHROUGH FLUIDIZED RARE EARTH CATALYST” which issued on Apr. 25, 1972 toWilliam Q. Beard, Jr. and U.S. Pat. No. 3,702,311 entitled“HALODEHYDROGENATION CATALYST” which issued on Nov. 7, 1972 to WilliamQ. Beard, Jr. both describe a process for production of vinyl halides ina three reactor system combining a halodehydrogenation reactor, anoxyhalogenation reactor and a dehydrohalogenation reactor. The authorsdescribe the halodehydrogenation of ethane to produce ethylene forsubsequent conversion to EDC through oxyhalogenation (oxychlorination)with subsequent production of VCM through conventional thermal cracking.HCl produced in the cracking operation is returned to theoxyhalogenation reactor in '934 and to the halodehydrogenation reactorin '311. In the latter patent, the advantages of excess total chlorine,as both HCl and Cl₂ are shown to augment yield of desirable products.

U.S. Pat. No. 3,644,561 entitled “OXYDEHYDROGENATION OF ETHANE” whichissued on Feb. 22, 1972 to William Q. Beard, Jr. and U.S. Pat. No.3,769,362 entitled “OXYDEHYDROGENATION OF ETHANE” which issued on Oct.30, 1973 to William Q. Beard, Jr. relate closely to those above anddescribe processes for the oxydehydrogenation of ethane to ethylene inthe presence of excess quantities of hydrogen halide. The patentdescribes a catalyst of either copper or iron halide further stabilizedwith rare earth halide where the ratio of rare earth to copper or ironhalide is greater than 1:1. The patent describes use of a substantialexcess of HCl relative to the molar amount of ethane fed, the HCl beingunconsumed in the reaction.

U.S. Pat. No. 4,046,823 entitled “PROCESS FOR PRODUCING1,2-DICHLOROETHANE” which issued on Sep. 6, 1977 to Ronnie D. Gordon andCharles M. Starks describes a process for the production of EDC whereethane and chlorine are reacted in the gas-phase over a coppercontaining catalyst.

U.S. Pat. No. 4,100,211 entitled “PROCESS FOR PREPARATION OF ETHYLENEAND VINYL CHLORIDE FROM ETHANE” which issued on Jul. 11, 1978 to AngeloJoseph Magistro describes regeneration of an iron catalyst for a processwhich reacts ethane into both ethylene and VCM in a mixture. This patentdescribes that a chlorine source is present from 0.1 mole to 10 molesper mole of ethane. In general, as the ratio of hydrogen chloride toethane is increased, the yield of vinyl chloride and other chlorinatedproducts also increases even as the yield of ethylene decreases.

U.S. Pat. No. 4,300,005 entitled “PREPARATION OF VINYL CHLORIDE” whichissued on Nov. 10, 1981 to Tao P. Li suggests a copper-based catalystfor production of VCM in the presence of excess HCl.

U.S. Pat. No. 5,097,083 entitled “PROCESS FOR THE CHLORINATION OFETHANE” which issued on Mar. 17, 1992 to John E. Stauffer describeschlorocarbons as a chlorine source in an ethane-to-VCM process. Thispatent describes methods where chlorohydrocarbons may be used to captureHCl for subsequent use in the production of vinyl.

EVC Corporation has been active in ethane-to-vinyl technology, and thefollowing four patents have resulted from their efforts in development.

EP 667,845 entitled “OXYCHLORINATION CATALYST” which issued on Jan. 14,1998 to Ray Hardman and Ian Michael Clegg describes a copper-basedcatalyst with a stabilization package for ethane-to-vinyl catalysis.This catalyst appears to be relevant to the further technology describedin the following three US patents.

U.S. Pat. No. 5,663,465 entitled “BY-PRODUCT RECYCLING INOXYCHLORINATION PROCESS” which issued on Sep. 2, 1997 to Ian MichaelClegg and Ray Hardman describes a method for the catalyticoxychlorination of ethane to VCM which combines ethane and a chlorinesource in an oxychlorination reactor with a suitable catalyst; recyclesthe byproducts to the oxychlorination reactor; treats unsaturatedchlorinated hydrocarbon byproducts in a hydrogenation step to convertthem to their saturated counterparts and passes them back to thereactor; and chlorinates ethylene byproduct to 1,2-dichloroethane forrecycle.

U.S. Pat. No. 5,728,905 entitled “VINYL CHLORIDE PRODUCTION PROCESS”which issued on Mar. 17, 1998 to Ian Michael Clegg and Ray Hardmandiscusses ethane-to-vinyl manufacture in the presence of excess HClusing a copper catalyst. The patent describes a process of catalyticoxychlorination of ethane between ethane, an oxygen source and achlorine source in the presence of a copper and alkali metal-containingcatalyst. HCl is supplied to the oxychlorination reactor in excess ofthe stoichiometric requirement for chlorine.

U.S. Pat. No. 5,763,710 entitled “OXYCHLORINATION PROCESS” which issuedon Jun. 9, 1998 to Ian Michael Clegg and Ray Hardman discusses catalyticoxychlorination of ethane to VCM by combining ethane and a chlorinesource in an oxychlorination reactor in the presence of anoxychlorination catalyst (the reaction conditions selected to maintainan excess of HCl); separating the VCM products; and recyclingby-products to the reactor.

Turning now to art in the derivation of vinyl chloride from ethylene,most commercial processes for the production of VCM use ethylene andchlorine as key raw materials. Ethylene is contacted with chlorine inliquid 1,2-dichloroethane containing a catalyst in a direct chlorinationreactor. The 1,2-dichloroethane is subsequently cracked at elevatedtemperature to yield VCM and hydrogen chloride (HCl). The HCl producedis in turn fed to an oxychlorination reactor where it is reacted withethylene and oxygen to yield more 1,2-dichloroethane. This1,2-dichloroethane is also fed to thermal cracking to produce VCM. Sucha process is described in U.S. Pat. No. 5,210,358 entitled “CATALYSTCOMPOSITION AND PROCESS FOR THE PREPARATION OF ETHYLENE FROM ETHANE”which issued on May 11, 1993 to Angelo J. Magistro.

The three unit operations (direct chlorination, oxychlorination andthermal cracking) of most presently used commercial processes arefrequently referenced in combination as a “balanced” EDC plant, althoughadditional sources of chlorine (HCl) are, in one embodiment, alsobrought into these extended plant systems. The net stoichiometry of the“balanced” plant is:4C₂H₄+2Cl₂+O₂→4C₂H₃Cl+2H₂O

Ethylene cost represents a significant fraction of the total cost ofproduction of VCM and requires expensive assets to produce. Ethane isless expensive than ethylene, and production of VCM from ethane should,therefore, reasonably lower the production cost of VCM in comparison tothe production cost of VCM when manufactured primarily from purified andseparated ethylene.

It is common to refer to the conversion of ethylene, oxygen and hydrogenchloride to 1,2-dichloroethane as oxychlorination. Catalysts for theproduction of 1,2-dichloroethane by oxychlorination of ethylene sharemany common characteristics. Catalysts capable of performing thischemistry have been classified as modified Deacon catalysts [Olah, G.A., Molnar, A., Hydrocarbon Chemistry, John Wiley & Sons (New York,1995), pg 226]. Deacon chemistry refers to the Deacon reaction, theoxidation of HCl to yield elemental chlorine and water. Other authorshave offered that oxychlorination is the utilization of HCl forchlorination and that the HCl is converted oxidatively into Cl₂ by meansof the Deacon process [Selective Oxychlorination of Hydrocarbons: ACritical Analysis, Catalytica Associates, Inc., Study 4164A, October1982, page 1]. The ability of oxychlorination catalysts to produce freechlorine (Cl₂) thus defines them. Indeed, oxychlorination of alkanes hasbeen linked to the production of free chlorine in the system [SelectiveOxychlorination of Hydrocarbons: A Critical Analysis, CatalyticalAssociates, Inc., Study 4164A, October 1982, page 21 and referencestherein]. These catalysts employ supported metals capable of accessingmore than one stable oxidation state, such as copper and iron. In theconventional technology, oxychlorination is the oxidative addition oftwo chlorine atoms to ethylene from HCl or another reduced chlorinesource.

Production of vinyl from ethane can proceed via oxychlorination providedcatalysts are present which are capable of production of free chlorine.Such catalysts will convert ethylene to 1,2-dichloroethane at lowtemperatures. At higher temperatures, 1,2-dichloroethane will bedisposed to thermally crack to yield HCl and vinyl chloride.Oxychlorination catalysts chlorinate olefinic materials to still higherchlorocarbons. Thus, just as ethylene is converted to1,2-dichloroethane, vinyl chloride is converted to1,1,2-trichloroethane. Processes using oxychlorination catalystsinherently produce higher chlorinated side-products. This is examined ingreat detail in patents to EVC (EP 667,845, U.S. Pat. No. 5,663,465,U.S. Pat. No. 5,728,905, and U.S. Pat. No. 5,763,710), which show highlevels of multichlorinated side-products being produced over theoxychlorination catalyst used. In consideration of the above, a numberof concepts regarding the use of ethane to produce VCM have clearly beendescribed previously. Catalysts employed most frequently are modifiedDeacon catalysts operated at sufficiently higher temperatures (>400° C.)than those required to perform ethylene oxychlorination (<275° C.).Catalysts used for ethane-to-VCM manufacture are frequently stabilizedagainst the migration of the first-row transition metals, as describedand reviewed in GB Patent 1,492,945; GB Patent 2,101,596; U.S. Pat. No.3,644,561; U.S. Pat. No. 4,300,005; and U.S. Pat. No. 5,728,905.

Use of chlorocarbons as chlorine sources in ethane-to-VCM processes hasbeen disclosed in GB Patent 1,039,369; GB Patent 2,101,596; U.S. Pat.No. 5,097,083; U.S. Pat. No. 5,663,465; and U.S. Pat. No. 5,763,710. GBPatent 1,039,369 requires that water be fed to the reactor system. GBPatent 2,101,596 is specific to copper catalysts. U.S. Pat. No.5,663,465 describes a process which uses a direct chlorination step toconvert ethylene to EDC prior to feeding it back to the VCM reactor.

Notwithstanding a relatively qualitative reference in GB Patent2,095,242, another recent development in ethylene-to-vinyl processes isoutlined in Dow Case No. 44649 to Mark E. Jones, Michael M. Olken, andDaniel A. Hickman, entitled “A PROCESS FOR THE CONVERSION OF ETHYLENE TOVINYL CHLORIDE, AND NOVEL CATALYST COMPOSITIONS USEFUL FOR SUCHPROCESS”, filed on Oct. 3, 2000 in the United States Receiving Office,Express Mail Mailing Number EL636832801US. The catalyst of thisapplication demonstrates utility in reacting significant quantities ofboth ethane and ethylene into vinyl chloride monomer and thereby opens adoor to new approaches in processes for vinyl chloride manufacture.However, the catalyst action yields hydrogen chloride in the reactionproduct. In this regard, management of hydrogen chloride (and affiliatedhydrochloric acid) within the process is a key issue to be resolved whena catalyst system capable of conversion of both ethane and ethylene intovinyl chloride monomer is used. In contemplation of vinyl chloridefacility construction, there is also a need to enable use of priorequipment as much as possible, where some existing equipment may havethe ability to handle hydrogen chloride and other existing equipmentdoes not have the ability to handle hydrogen chloride. The presentinvention provides embodiments for fulfilling these needs, by providingan apparatus and process for handling hydrogen chloride generated fromthe ethane/ethylene-to-vinyl reactor by essentially fully recovering itfrom the reactor effluent in the first unit operation after theethane/ethylene-to-vinyl reaction step or stage.

The invention provides a method of manufacturing vinyl chloride, usingthe steps of:

-   generating a reactor effluent stream by catalytically reacting    together ethane, ethylene, oxygen, and at least one chlorine source    of hydrogen chloride, chlorine, or a chlorohydrocarbon, where the    molar ratio of the ethane to the ethylene is between 0.02 and 50;-   cooling and condensing the reactor effluent stream to provide a raw    product stream having a first portion of the hydrogen chloride and a    raw cooled hydrogen chloride stream having a second portion of the    hydrogen chloride;-   separating the raw product stream into a vinyl chloride monomer    product stream and into a lights stream having the first portion of    the hydrogen chloride; and-   recycling the lights stream to catalytically react together with the    ethane, the ethylene, the oxygen, and the chlorine source in the    generating step.

The invention also provides a method of manufacturing vinyl chloride,comprising the steps of:

-   generating a reactor effluent stream by catalytically reacting    together ethane, ethylene, oxygen, and at least one chlorine source    of hydrogen chloride, chlorine, or a chlorohydrocarbon, wherein the    molar ratio of said ethane to said ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a vinyl chloride monomer    product stream and into a lights stream having said first portion of    said hydrogen chloride; and-   recycling said lights stream to catalytically react together with    said ethane, said ethylene, said oxygen, and said chlorine source in    said generating step.

The invention further provides a method of manufacturing vinyl chloride,comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream, a    vinyl chloride monomer product stream, an ethyl chloride stream, a    cis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant; and-   recycling said lights stream to said reactor.

The invention further provides a method of manufacturing vinyl chloride,comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream, a    vinyl chloride monomer product stream, an ethyl chloride stream, a    cis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant;-   dividing said lights stream into a purge stream and a recycle gas    stream;-   absorbing hydrogen chloride from said purge stream to separate an    aqueous hydrogen chloride stream;-   combining said aqueous hydrogen chloride stream with said raw cooled    hydrogen chloride stream;-   absorbing and recycling to said reactor a C2 stream from said purge    stream; and-   recycling said recycle gas stream to said reactor.

The invention further provides a method of manufacturing vinyl chloride,comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream, a    vinyl chloride monomer product stream, an ethyl chloride stream, a    cis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant;-   dividing said lights stream into a purge stream and a recycle gas    stream;-   absorbing hydrogen chloride from said purge stream to separate an    aqueous hydrogen chloride stream;-   combining said aqueous hydrogen chloride stream with said raw cooled    hydrogen chloride stream;-   hydrogenating said cis-1,2-dichloroethylene and    trans-1,2-dichloroethylene blended stream to provide recycle feed to    said reactor,-   absorbing and recycling to said reactor a C2 stream from said purge    stream; and-   recycling said recycle gas stream to said reactor.

The invention further provides an apparatus for manufacturing vinylchloride, comprising:

-   a reactor for generating a reactor effluent stream by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   means for cooling and condensing said reactor effluent stream to    provide a raw product stream having a first portion of said hydrogen    chloride and a raw cooled hydrogen chloride stream having a second    portion of said hydrogen chloride;-   means for separating said raw product stream into a vinyl chloride    monomer product stream and into a lights stream having said first    portion of said hydrogen chloride; and-   means for recycling said lights stream to said reactor.

The invention further provides an apparatus for manufacturing vinylchloride, comprising:

-   a reactor for generating a reactor effluent stream by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   means for cooling and condensing said reactor effluent stream to    provide a raw product stream having a first portion of said hydrogen    chloride and a raw cooled hydrogen chloride stream having a second    portion of said hydrogen chloride;-   means for separating said raw product stream into a water product    stream, a vinyl chloride monomer product stream, an ethyl chloride    stream, a cis-1,2-dichloroethylene and trans-1,2-dichloroethylene    blended stream, a 1,2-dichloroethane stream, a heavies stream, and a    lights stream having said first portion of said hydrogen chloride;-   means for recovering an anhydrous hydrogen chloride stream from said    raw cooled hydrogen chloride stream;-   means for recycling said anhydrous hydrogen chloride stream to said    reactor as said hydrogen chloride reactant; and-   means for recycling said lights stream to said reactor.

The invention further provides an apparatus for manufacturing vinylchloride, comprising:

-   a reactor for generating a reactor effluent stream by catalytically    reacting together, ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   means for cooling and condensing said reactor effluent stream to    provide a raw product stream having a first portion of said hydrogen    chloride and a raw cooled hydrogen chloride stream having a second    portion of said hydrogen chloride;-   means for separating said raw product stream into a water product    stream, a vinyl chloride monomer product stream, an ethyl chloride    stream, a cis-1,2-dichloroethylene and trans-1,2-dichloroethylene    blended stream, a 1,2-dichloroethane stream, a heavies stream, and a    lights stream having said first portion of said hydrogen chloride;-   means for recovering an anhydrous hydrogen chloride stream from said    raw cooled hydrogen chloride stream;-   means for recycling said anhydrous hydrogen-chloride stream to said    reactor as said hydrogen chloride reactant;-   means for dividing said lights stream into a purge stream and a    recycle gas stream;-   means for absorbing hydrogen chloride from said purge stream to    separate an aqueous hydrogen chloride stream;-   means for combining said aqueous hydrogen chloride stream with said    raw cooled hydrogen chloride stream;-   means for absorbing and recycling to said reactor a C2 stream from    said purge stream; and-   means for recycling said recycle gas stream to said reactor.

The invention further provides an apparatus for manufacturing vinylchloride, comprising:

-   a reactor for generating a reactor effluent stream by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   means for cooling and condensing said reactor effluent stream to    provide a raw product stream having a first portion of said hydrogen    chloride and a raw cooled hydrogen chloride stream having a second    portion of said hydrogen chloride;-   means for separating said raw product stream into a water product    stream, a vinyl chloride monomer product stream, an ethyl chloride    stream, a cis-1,2-dichloroethylene and trans-1,2-dichloroethylene    blended stream, a 1,2-dichloroethane stream, a heavies stream, and a    lights stream having said first portion of said hydrogen chloride;-   means for recovering an anhydrous hydrogen chloride stream from said    raw cooled hydrogen chloride stream;-   means for recycling said anhydrous hydrogen chloride stream to said    reactor as said hydrogen chloride reactant;-   means for dividing said lights stream into a purge stream and a    recycle gas stream;-   means for absorbing hydrogen chloride from said purge stream to    separate an aqueous hydrogen chloride stream;-   means for combining said aqueous hydrogen chloride stream with said    raw cooled hydrogen chloride stream;-   means for hydrogenating said cis-1,2-dichloroethylene and    trans-1,2-dichloroethylene blended stream to provide recycle feed to    said reactor;-   means for absorbing and recycling to said reactor a C2 stream from    said purge stream; and-   means for recycling said recycle gas stream to said reactor.

The invention further provides vinyl chloride manufactured using aprocess comprising the steps of:

-   generating a reactor effluent stream by catalytically reacting    together ethane, ethylene, oxygen, and at least one chlorine source    of hydrogen chloride, chlorine, or a chlorohydrocarbon, wherein the    molar ratio of said ethane to said ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a vinyl chloride monomer    product stream and into a lights stream having said first portion of    said hydrogen chloride; and-   recycling said lights stream to catalytically react together with    said ethane, said ethylene, said oxygen, and said chlorine source in    said generating step.

The invention further provides vinyl chloride manufactured using aprocess comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream, a    vinyl chloride monomer product stream, an ethyl chloride stream, a    cis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant; and-   recycling said lights stream to said reactor.

The invention further provides vinyl chloride manufactured using aprocess comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream, a    vinyl chloride monomer product stream, an ethyl chloride stream, a    cis-1,2 dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant;-   dividing said lights stream into a purge stream and a recycle gas    stream;-   absorbing hydrogen chloride from said purge stream to separate an    aqueous hydrogen chloride stream;-   combining said aqueous hydrogen chloride stream with said raw cooled    hydrogen chloride stream;-   absorbing and recycling to said reactor a C2 stream from said purge    stream; and-   recycling said recycle gas stream to said reactor.

The invention further provides vinyl chloride manufactured using aprocess comprising the steps of:

-   generating a reactor effluent stream from a reactor by catalytically    reacting together ethane, ethylene, oxygen, and at least one    chlorine source of hydrogen chloride, chlorine, or a    chlorohydrocarbon, wherein the molar ratio of said ethane to said    ethylene is between 0.02 and 50;-   cooling and condensing said reactor effluent stream to provide a raw    product stream having a first portion of said hydrogen chloride and    a raw cooled hydrogen chloride stream having a second portion of    said hydrogen chloride;-   separating said raw product stream into a water product stream a    vinyl chloride monomer product stream, an ethyl, chloride stream, a    cis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended    stream, a 1,2-dichloroethane stream, a heavies stream, and a lights    stream having said first portion of said hydrogen chloride;-   recovering an anhydrous hydrogen chloride stream from said raw    cooled hydrogen chloride stream;-   recycling said anhydrous hydrogen chloride stream to said reactor as    said hydrogen chloride reactant;-   dividing said lights stream into a purge stream and a recycle gas    stream;-   absorbing hydrogen chloride from said purge stream to separate an    aqueous hydrogen chloride stream;-   combining said aqueous hydrogen chloride stream with said raw cooled    hydrogen chloride stream;-   hydrogenating said cis-1,2-dichloroethylene and    trans-1,2-dichloroethylene blended stream to provide recycle feed to    said reactor;-   absorbing and recycling to said reactor a C2 stream from said purge    stream; and-   recycling said recycle gas stream to said reactor.

Additional features and advantages of the present invention are morefully apparent from a reading of the detailed description of thepreferred embodiments and the accompanying drawings in which:

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows characterization, as best understood from earlierpublications, of a contemplated ethane-to-vinyl chloride processemploying a catalyst capable of converting ethane to VCM.

FIG. 2 shows an ethane/ethylene-to-vinyl chloride process employing acatalyst capable of converting ethane and ethylene to VCM viaoxydehydro-chlorination.

FIG. 3 modifies the oxydehydro-chlorination process of FIG. 2 to showfurther hydrogenation of cis-dichloroethylene and trans-dichloroethylenestreams to 1,2-dichloroethane.

As noted in the Background discussion of the present specification,oxychlorination is conventionally referenced as the oxidative additionof two chlorine atoms to ethylene from HCl or other reduced chlorinesource. Catalysts capable of performing this chemistry have beenclassified as modified Deacon catalysts [Olah, G. A., Molnar, A.,Hydrocarbon Chemistry, John Wiley & Sons (New York, 1995), pg 226].Deacon chemistry refers to the Deacon reaction, the oxidation of HCl toyield elemental chlorine and water.

In contrast to oxychlorination, the preferred process described hereinpreferably utilizes oxydehydro-chlorination in convertingethane-containing and ethylene-containing streams to VCM at highselectivity. Oxydehydro-chlorination is the conversion of a hydrocarbon,using oxygen and a chlorine source, to a chlorinated hydrocarbon whereinthe carbons either maintain their initial valence or have their valencyreduced (that is, sp³ carbons remain sp³ or are converted to sp², andsp² carbons remain sp² or are converted to sp). This differs from theconventional definition of oxychlorination whereby ethylene is convertedto 1,2-dichloroethane, using oxygen and a chlorine source, with a netincrease in carbon valency (that is, sp² carbons are converted to sp³carbons). Given the ability of the catalyst to convert ethylene to vinylchloride, it is advantageous to recycle ethylene produced in theoxydehydro-chlorination reaction process back to the reactor. Thebyproducts produced in the oxydehydro-chlorination reactor include ethylchloride, 1,2-dichloroethane, cis-1,2-dichloroethylene andtrans-1,2-dichloroethylene. The oxydehydro-chlorination catalyst is alsoan active catalyst for the elimination of HCl from saturatedchlorohydrocarbons. Recycle of ethyl chloride and 1,2-dichloroethane is,in some cases, advantageously employed in the production of vinylchloride. The remaining significant chlorinated organic side-productsare the dichloroethylenes. These materials are, in one embodiment,hydrogenated to yield 1,2-dichloroethane. 1,2-dichloroethane is a largevolume chemical and is either sold or recycled. In an alternativeembodiment, EDC is hydrogenated completely to yield ethane and HCl.Intermediate severity hydrogenations yield mixtures of1,2-dichloroethane, ethane, ethyl chloride, and HCl; such mixtures arealso appropriate for recycle to the oxydehydro-chlorination reactor.

Turning now to consideration of FIG. 1, for ethane-to-vinyl conversionas best understood from earlier publications, Ethane to VCM Process 100shows characterization of a contemplated ethane-to-vinyl chlorideprocess employing a catalyst capable of converting ethane to VCM; inthis regard, the process does not provide for input of significantquantities of ethylene from either recycle streams or feed-streams tothe ethane-VCM reactor (Ethane Reactor 102). It should also be notedthat, since an ethane-to-vinyl manufacturing system of appropriatenormal manufacturing scale has not, to the best knowledge of theinventors, been yet constructed, proposed process approaches are theonly sources for embodiments which have been previously conceptualized.In this regard, Process 100 is a unified and simplified approximation toprocesses collectively reviewed in several publications respective toinvestigations and developments at EVC Corporation: VinylChloride/Ethylene Dichloride 94/95-5 (August, 1996; Chemical Systems,Inc.; Tarrytown, N.Y.); EP 667,845; U.S. Pat. No. 5,663,465; U.S. Pat.No. 5,728,905; and U.S. Pat. No. 5,763,710.

In consideration of the details shown in FIG. 1, Ethane Reactor 102outputs a fluid stream to Quench Column 106 where HCl is quenched fromthe reactor output effluent. Quench Column 106 forwards a raw strong HClaqueous stream to Phase Separation Subsystem 108. Phase SeparationSubsystem 108 outputs a fluid stream to Anhydrous HCl Recovery Subsystem110 where aqueous hydrogen chloride (hydrochloric acid), anhydrous HCl,and water are separated from the raw strong HCl aqueous stream.

Anhydrous HCl Recovery Subsystem 110 outputs Stream 130 to recycleanhydrous hydrogen chloride to Ethane Reactor 102, and Anhydrous HClRecovery Subsystem 110 also outputs water (for subsequent use or towaste recovery). Anhydrous HCl Recovery Subsystem 110 returns arelatively dilute aqueous stream of HCl (hydrochloric acid) via Stream128 to Quench Column 106. Quench Column 106 also outputs a fluid streamto Lights Column 114 where a lights stream containing ethylene isfurther removed from the reactor effluent product stream.

Lights Column 114 outputs the lights stream to Direct ChlorinationReactor 112 where chlorine (Stream 126) is added to directly chlorinateethylene in the lights stream into EDC (1,2-dichloroethane). EDC isrecovered in EDC Recovery Column 116 for recycle to Ethane Reactor 102,and a certain amount of the remaining lights gas is recycled to EthaneReactor 102 as Stream 134 with CO (carbon monoxide) compositioninstrumentation providing a measurement (not shown) for use in a controlsystem's (not shown) determination of an appropriate portion of theremaining lights gas for processing via Vent Oxidation Unit 118 togenerate a vent stream for removal of CO, CO₂, and other impurities fromthe system.

Effluent from Lights Column 114 which does not proceed to DirectChlorination Reactor 112 forwards (a) first, to Drying Subsystem 120 forremoval of water; (b) further, to VCM Purification Column 122 forseparation of VCM (vinyl chloride monomer) product; and then (c)further, to Heavies Column 124 for removal of heavies and generation ofStream 132. Stream 132 is a blended fluid of cis-1,2-dichloroethyleneand trans-1,2-dichloroethylene, 1,2-dichloroethane, ethyl chloride, andother chlorinated organics. In an alternative contemplated embodimentbased upon consideration of the literature, Drying Subsystem 120 removeswater prior to Lights Column 114, with the VCM-carrying effluent fromLights Column 114 being forwarded (a) first, to VCM Purification Column122 for separation of VCM (vinyl chloride monomer) product and then (b)further, to Heavies Column 124 for removal of heavies and generation ofStream 132.

Finally, Stream 132 forwards to RCl (chlorinated organics) HydrogenationReactor 104 where addition of hydrogen effects a recycle stream forforwarding to Ethane Reactor 102.

Turning now to consideration of FIG. 2, according to the preferredembodiments of the present specification, Ethane to VCMOxydehydro-chlorination Process 200 shows an ethane/ethylene-to-vinylchloride process employing a catalyst capable of converting ethane andethylene to VCM via oxydehydro-chlorination; in this regard, the processprovides for input of significant quantities of both ethane and ethylenefrom either recycle streams or feed-streams to the reactor(Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202).Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 receivesinput from (a) feed streams Ethane Feed Stream 222, HCl Feed Stream 224,Oxygen Feed Stream 226, and Chlorine Feed Stream 228 and (b) recyclestreams Ethyl Chloride Stream 230, Hydrogen chloride (HCl) Stream 266,and lights recycle Stream 248 as well a portion of EDC Stream 262 whenEDC is advantageously used for recycle according to the market andoperational conditions at a particular moment of manufacture.

As reflected in Dow Case No. 44649 to Mark E. Jones, Michael M. Olken,and Daniel A. Hickman, entitled “A PROCESS FOR THE CONVERSION OFETHYLENE TO VINYL CHLORIDE, AND NOVEL CATALYST COMPOSTIONS USEFUL FORSUCH PROCESS”, filed on Oct. 3, 2000 in the United States ReceivingOffice, Express Mail Mailing Number EL636832801US, the catalyst used inEthane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 comprises atleast one rare earth material. The rare earths are a group of 17elements consisting of scandium (atomic number 21), yttrium (atomicnumber 39) and the lanthanides (atomic numbers 57-71) [James B. Hedrick,U.S. Geological Survey—Minerals Information—1997, “Rare-Earth Metals”].The catalyst can be provided as either a porous, bulk material or it canbe supported on a suitable support. Preferred rare earth materials arethose based on lanthanum, cerium, neodymium, praseodymium, dysprosium,samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium,europium, thulium, and lutetium. Most preferred rare earth materials foruse in the aforementioned VCM process are based on those rare earthelements which are typically considered as being single valencymaterials. Catalytic performance of multi-valency materials appears tobe less desirable than those that are single valency. For example,cerium is known to be an oxidation-reduction catalyst having the abilityto access both the 3⁺ and 4⁺ stable oxidation states. This is one reasonwhy, if the rare earth material is based on cerium, the catalyst furthercomprises at least one more rare earth element other than cerium.Preferably, if one of the rare earths employed in the catalyst iscerium, the cerium is provided in a molar ratio that is less than thetotal amount of other rare earths present in the catalyst. Morepreferably, however, substantially no cerium is present in the catalyst.By “substantially no cerium” it is meant that any cerium is in an amountless than 33 atom percent of the rare earth components, preferably lessthan 20 atom percent, and most preferably less than 10 atom percent.

The rare earth material for the catalyst is more preferably based uponlanthanum, neodymium, praseodymium or mixtures of these. Mostpreferably, at least one of the rare earths used in the catalyst islanthanum. Furthermore, for the ethylene-containing feed to VCM processof this invention, the catalyst is substantially free of iron andcopper. In general, the presence of materials that are capable ofoxidation-reduction (redox) is undesirable for the catalyst. It ispreferable for the catalyst to also be substantially free of othertransition metals that have more than one stable oxidation state. Forexample, manganese is another transition metal that is preferablyexcluded from the catalyst. By “substantially free” it is meant that theatom ratio of rare earth element to redox metal in the catalyst isgreater than 1, preferably greater than 10, more preferably greater than15, and most preferably greater than 50.

As stated above, the catalyst may also be deposited on an inert support.Preferred inert supports include alumina, silica gel, silica-alumina,silica-magnesia, bauxite, magnesia, silicon carbide, titanium oxide,zirconium oxide, zirconium silicate, and combinations thereof. However,in a most preferred embodiment, the support is not a zeolite. When aninert support is utilized, the rare earth material component of thecatalyst typically comprises from 3 weight percent (wt percent) to 85 wtpercent of the total weight of the catalyst and support. The catalystmay be supported on the support using methods already known in the art.

It may also be advantageous to include other elements within thecatalyst in both of the porous, bulk material and supported forms. Forexample, preferable elemental additives include alkaline earths, boron,phosphorous, sulfur, silicon, germanium, titanium, zirconium, hafnium,aluminum, and combinations thereof. These elements can be present toalter the catalytic performance of the composition or to improve themechanical properties (for example attrition-resistance) of thematerial.

Prior to combining the ethylene-containing feed, oxygen source, andchlorine source in the reactor for the VCM process embodiment of thisinvention, it is preferable for the catalyst composition to comprise asalt of at least one rare earth element with the proviso that thecatalyst is substantially free of iron and copper and with the furtherproviso that when cerium is employed the catalyst further comprises atleast one more rare earth element other than cerium. The salt of atleast one rare earth element is preferably selected from rare earthoxychlorides, rare earth chlorides, rare earth oxides, and combinationsthereof, with the proviso that the catalyst is substantially free ofiron and copper and with the further proviso that when cerium is usedthe catalyst further comprises at least one more rare earth elementother than cerium. More preferably, the salt comprises a rare earthoxychloride of the formula MOCl, wherein M is at least one rare earthelement chosen from lanthanum, cerium, neodymium, praseodymium,dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium) holmium,terbium, europium, thulium, lutetium, or mixtures thereof, with theproviso that, when cerium is present, at least one more rare earthelement other than cerium is also present. Most preferably, the salt isa porous, bulk lanthanum oxychloride (LaOCl) material. As has beenmentioned, this material beneficially does not undergo gross changes(for example, fracturing) when chlorinated in situ in this process, andprovides the further beneficial property of water solubility in thecontext of this process after a period of use (LaOCl is initiallywater-insoluble), so that should spent catalyst need to be removed froma fluidized bed, fixed bed reactor or other process equipment orvessels, this can be done without hydroblasting or conventionallabor-intensive mechanical techniques by simply flushing the spentcatalyst from the reactor in question with water.

Typically, when the salt is a rare earth oxychloride (MOCl), it has aBET surface area of at least 12 m²/g, preferably at least 15 m²/g, morepreferably at least 20 m²/g, and most preferably at least 30 m²/g.Generally, the BET surface area is less than 200 m²/g. For these abovemeasurements, the nitrogen adsorption isotherm was measured at 77K andthe surface area was calculated from the isotherm data utilizing the BETmethod (Branauer, S., Emmett, P. H., and Teller, E., J. Am. Chem. Soc.,60, 309 (1938)). In addition, it is noted that the MOCl phases possesscharacteristic powder X-Ray Diffraction (XRD) patterns that are distinctfrom the MCl₃ phases.

It is also possible, as indicated in several instances previously, tohave mixtures of the rare earths (“M”) within the MOCl composition. Forexample, M can be a mixture of at least two rare earths selected fromlanthanum, cerium, neodymium, praseodymium, dysprosium, samarium,yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium,thulium and lutetium. Similarly, it is also possible to have mixtures ofdifferent MOCl compositions wherein M is different as between eachcomposition of the MOCl's in the mixture.

Once the ethylene-containing feed, oxygen source, and chlorine sourceare combined in the reactor, a catalyst is formed in situ from the saltof at least one rare earth element. In this regard, it is believed thatthe in situ formed catalyst comprises a chloride of the rare earthcomponent. An example of such a chloride is MCl₃, wherein M is a rareearth component selected from lanthanum, cerium, neodymium,praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium,ytterbium, holmium, terbium, europium, thulium, lutetium and mixturesthereof, with the proviso that when cerium is present the catalystfurther comprises at least one more rare earth element other thancerium. Typically, when the salt is a rare earth chloride (MCl₃), it hasa BET surface area of at least 5 m²/g, preferably at least 10 m²/g, morepreferably at least 15 m²/g, more preferably at least 20 m²/g, and mostpreferably at least 30 m²/g.

In light of the disclosure herein, those of skill in the art willundoubtedly recognize alternative methods for preparing useful catalystcompositions. A method currently felt to be preferable for forming thecomposition comprising the rare earth oxychloride (MOCl) comprises thefollowing steps: (a) preparing a solution of a chloride salt of the rareearth element or elements in a solvent comprising either water, analcohol, or mixtures thereof; (b) adding a nitrogen-containing base tocause the formation of a precipitate; and (c) collecting, drying andcalcining the precipitate in order to form the MOCl material. Typically,the nitrogen-containing base is selected from ammonium hydroxide, allylamine, aryl amine, arylalkyl amine, alkyl ammonium hydroxide, arylammonium hydroxide, arylalkyl ammonium hydroxide, and mixtures thereof.The nitrogen-containing base may also be provided as a mixture of anitrogen-containing base with other bases that do not contain nitrogen.Preferably, the nitrogen-containing base is tetra-alkyl ammoniumhydroxide. The solvent in Step (a) is preferably water. Drying of thecatalytically-useful composition can be done in any manner, including byspray drying, drying in a purged oven and other known methods. For thepresently-preferred fluidized bed mode of operation, a spray-driedcatalyst is preferred.

A method currently felt to be preferable for forming the catalystcomposition comprising the rare earth chloride (MCl₃) comprises thefollowing steps: (a) preparing a solution of a chloride salt of the rareearth element or elements in a solvent comprising either water, analcohol, or mixtures thereof; (b) adding a nitrogen-containing base tocause the formation of a precipitate; (c) collecting, drying andcalcining the precipitate; and (d) contacting the calcined precipitatewith a chlorine source. For example, one application of this method(using La to illustrate) would be to precipitate LaCl₃ solution with anitrogen containing base, dry it, add it to the reactor, heat it to 400°C. in the reactor to perform the calcination, and then contact thecalcined precipitate with a chlorine source to form the catalystcomposition in situ in the reactor. Catalysts for preferred use arefurther clarified by a consideration of examples presented in asubsequent section of this specification.

Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 catalyticallyreacts together ethane, ethylene, hydrogen chloride, oxygen, andchlorine along with at least one recycle stream to yield ReactorEffluent Stream 232; and it is of special note that the molar ratio ofethane to ethylene derived from all feeds to Ethane/Ethylene To VCMOxydehydro-chlorination Reactor 202 is between 0.02 and 50 (note thatthe particular operational ratio at any moment is determined by issuesin operational process status) without long-term detriment to catalystfunctionality. Depending on market and operational conditions at aparticular moment of manufacture, ethylene is added to Reactor 202 viaEthylene Stream 289. In this regard, a more preferred molar ratio ofethane to ethylene derived from all feeds to Ethane/Ethylene To VCMOxydehydro-chlorination Reactor 202 is between 0.1 and 10. When marketand operational conditions (at a particular moment of manufacture)permit, the most preferred mode is for Ethylene Stream 289 to have aflow of zero and for the molar ratio of ethane to ethylene derived fromall feeds to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202to be between 0.3 and 4, with variance therein dependent upon localprocess conditions and catalyst life-cycle considerations. Even as theReactor 202 effluent stream (Stream 232) is generated by catalyticallyreacting together ethane, ethylene, oxygen, and at least one chlorinesource of hydrogen chloride, chlorine, or a chlorohydrocarbon, it is tobe noted that catalyst selectivity in the conversion of these streams toVCM benefits by, first, conditioning lanthanide-based catalysts withelemental chlorine. Catalyst selectivity in the conversion of thesestreams to VCM using lanthanide-based catalysts also benefits whenelemental chlorine (Steam 228) is included as a portion of the chlorinesource to Reactor 202. It should also be noted that any other catalystsystems, which exhibit the capacity to convert both ethane and ethyleneto VCM, are advantageously, in alternative embodiments, also used withthe VCM process and apparatus herein disclosed.

Chlorine sources (selected from hydrogen chloride, chlorine, and achlorohydrocarbon) HCl Feed Stream 224, Chlorine Feed Stream 228, anyportion of EDC Stream 262 chosen for recycle, and any other recycled orraw material feed streams containing, without limitation, at least oneof a chlorinated methane or a chlorinated ethane (for example, withoutlimitation, carbon tetrachloride, 1,2-dichloroethane, ethyl chloride,1,1-dichloroethane, and 1,1,2-trichloroethane) collectively providechlorine to the oxydehydro-chlorination reaction; these streams areindividually variable from moment to moment in real-time operation forproviding the stoichiometric chlorine needed for VCM conversion. Withrespect to EDC (1,2-dichloroethane) from EDC Stream 262, marketconditions affecting the opportunity for direct sale determine theappropriate amount for either recycle to Reactor 202 or direct sale. Afurther option for use of a portion of EDC Stream 262, dependent uponthe particular facility, is for feedstock to a VCM conversion furnace.In this regard, operation of Process 200 is alternatively conducted sothat (a) 1,2-dichloroethane generated in Reactor 202 is purified forsale, (b) 1,2-dichloroethane generated in Reactor 202 is purified forrecycle to Reactor 202, and/or (c) 1,2-dichloroethane generated Reactor202 is purified for cracking in a vinyl furnace. It is also to be notedthat EDC is also, at occasional times, advantageously purchased for useas a chlorine source.

Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 outputsReactor Effluent Stream 232 to feed Cooling Condenser 204. CoolingCondenser 204 treats Reactor Effluent Stream 232 to provide (a) a rawproduct (vapor) stream having a first portion of hydrogen chloride and(b) a raw cooled (aqueous) hydrogen chloride stream having the remainderof the hydrogen chloride which exited Reactor 202; the raw product(vapor) stream is Stream 240.

Stream 234 is conveyed to Phase Separation Subsystem 206 for removal ofresidual organic compounds from the raw cooled HCl. Phase SeparationSubsystem 206 is, in alternative embodiments, a decanter, a stripper, ora combination of a decanter and stripper. From Phase SeparationSubsystem 206 the removed organic materials (essentially in liquidphase) are conveyed to Lights Column 210 via Stream 242, and theseparated raw cooled (essentially aqueous liquid) HCl is conveyed asStream 236 to Anhydrous HCl Recovery Subsystem 208. Anhydrous HClRecovery Subsystem 208 receives (aqueous) Stream 274 from Vent OxidationUnit (a thermal oxidation or other oxidation unit useful for vent streampurification to acceptable environmental compositions) 214, Stream 278(aqueous) from Lights HCl Absorption Unit 276, and (aqueous) Stream 236and generates output stream Stream 266 as anhydrous HCl recycle toEthane/Ethylene To VCM Oxydehydro-chlorination Reactor 202. Stream 268outputs water from Anhydrous HCl Recovery Subsystem 208 for subsequentuse or to waste recovery. In summary, Anhydrous HCl Recovery Subsystem208 provides functionality to recover an anhydrous hydrogen chloridestream from the raw cooled hydrogen chloride stream and other aqueousHCl streams of Process 200. Anhydrous HCl Recovery Subsystem 208 alsorecycles the anhydrous hydrogen chloride (vapor) stream to the reactor.As should be apparent to those of skill, there are other methodologiesfor separating anhydrous HCl from mixtures of water and HCl.

Cooling Condenser 204 also outputs Stream 240 (vapor) to Lights Column210 where a lights stream (vapor Stream 244) containing ethylene isfurther removed from the reactor effluent product stream. Note that, incontrast to the system discussed in FIG. 1, the ethylene from LightsColumn 210 is mostly returned as recycle to Ethane/Ethylene To VCMOxydehydro-chlorination Reactor 202 without conversion to EDC.

After separation of HCl and lights stream (Stream 244) from the reactoreffluent, Lights Column 210 forwards Stream 252 for separation of awater product stream, a vinyl chloride monomer product stream (Stream254), an ethyl chloride stream (Stream 230), a cis-1,2-dichloroethyleneand trans-1,2-dichloroethylene blended stream (Stream 260), a1,2-dichloroethane stream (Stream 262), and a heavies stream (Stream264). The manner of effecting these final separations is apparent tothose of skill, and a substantial number of classically-utilized processunits can be deployed in various configurations to achieve theseseparations. Drying Subsystem 216, VCM Purification Column 218, andHeavies Column 220 conveniently depict, therefore, the generalseparation systems (and, as such, should have the term “column”interpreted as a “virtual column” representing at least one physicalcolumn, although, in one contemplated embodiment, each column could beonly a single physical column) for separation of Water Stream 256, VCMProduct Stream 254, Ethyl Chloride Stream 230,Cis/trans-1,2-dichloroethylene Stream 260, and EDC Stream 262, withHeavies Stream 264 as organic material for destruction in a wasteorganic burner or use in an appropriate product where the generalproperties of Heavies Stream 264 are acceptable. In an alternativecontemplated embodiment, Drying Subsystem 216 removes water prior toLights Column 210, with the effluent from Lights Column 210 beingforwarded to VCM Purification Column 218. Note again that, with respectto EDC (1,2-dichloroethane) from EDC Stream 262, market conditionsaffecting the opportunity for direct sale function to determine theappropriate amount for either recycle to Reactor 202 or direct sale. Inthis regard, operation of VCM Purification Column 218, and HeaviesColumn 220 is alternatively conducted so that (a) 1,2-dichloroethane ispurified for sale, (b) 1,2-dichloroethane is purified for recycle toReactor 202, and/or (c) 1,2-dichloroethane is purified for cracking in avinyl furnace.

Returning now to Stream 244 as it exists from Lights Column 210, Stream244 is divided into a first stream portion forwarded directly in Stream248 to Ethane/Ethylene To VCM Oxydehydro-chlorination Reactor 202 andinto a second stream which forwards first to Lights HCl Absorption Unit276 and then to C2 Absorption and Stripping Columns 212. Lights HClAbsorption Unit 276 outputs aqueous HCl as Stream 278 to Anhydrous HClRecovery Subsystem 208. C2 Absorption and Stripping Columns 212 absorband strip C2 materials (ethane and ethylene) from the forwarded secondstream portion of Stream 244 and insure the recycle of the C2 materialsto Reactor 202 via C2 Recycle Stream 246 which, in combination the firststream portion from Stream 244, forms Stream 248. C2 Absorption andStripping Columns 212 also outputs a purge stream to Vent Oxidation Unit214 which outputs Vent Stream 250 to the atmosphere and also (aqueous)Stream 274 to Anhydrous HCl Recovery Subsystem 208. CO (carbon monoxide)composition instrumentation provides a measurement (not shown) for usein a control system's (not shown) determination of an appropriateportion of the remaining lights gas for processing via C2 Absorption andStripping Columns 212 and Vent Oxidation Unit 214 to generate VentStream 250 so that CO does not accumulate to unacceptable levels in theprocess.

Simulated relative stream flows and stream compositions for Ethane toVCM Oxydehydro-chlorination Process 200 are appreciated from aconsideration of Table 1. Table 1 (mass unit/time unit) data useslaboratory-derived catalyst performance measurements for lanthanumoxychloride at 400 degrees Celsius and essentially ambient pressure;further details on the preferred catalyst are appreciated from a studyof “A PROCESS FOR THE CONVERSION OF ETHYLENE TO VINYL CHLORIDE, ANDNOVEL CATALYST COMPOSITIONS USEFUL FOR SUCH PROCESS”. Table 1 shows someflows as a zero in the context of the simulation generating the data,but such a numeric value is not intended to mean a total absence of flowor absence of need for a stream Table 1 does not show Ethylene FeedStream 289; in this regard, and reprising an earlier point, when marketand operational conditions at a particular moment of manufacture permit,the most preferred mode is for Ethylene Stream 289 to have a flow ofzero. However, under certain conditions, Ethylene Stream 289 doescontribute an economically beneficial flow.

TABLE 1 ETHANE/ETHYLENE TO VINYL CHLORIDE MASS BALANCE FOR PROCESS 200Stream C₂H₆ C₂H₄ O₂ HCl Cl₂ Ar CO CO₂ EDC EtCl VCM DCE H₂O total 222 5720 0 0 0 0 0 0 0 0 0 0 0 572 224 0 0 0 0 0 0 0 0 0 0 0 0 0 0 226 0 0 5480 0 6 0 0 0 0 0 0 0 553 228 0 0 0 0 660 0 0 0 0 0 0 0 0 660 230 0 0 0 00 0 0 0 0 22 0 0 0 22 232 1847 1042 19 1459 0 98 1257 257 147 22 1000127 559 7834 234 83 27 0 510 0 0 2 7 142 15 428 116 553 1883 236 0 0 0510 0 0 0 0 0 0 0 0 553 1063 240 1765 1015 19 949 0 98 1255 251 5 7 57211 6 5951 242 83 27 0 0 0 0 2 7 142 15 428 116 0 820 244 1847 1042 19949 0 98 1257 257 0 0 0 0 0 5469 246 99 56 0 0 0 0 0 0 0 0 0 0 0 154 2481842 1039 18 896 0 93 1186 243 0 0 0 0 0 5316 250 0 0 0 0 0 6 0 150 0 00 0 13 168 252 0 0 0 0 0 0 0 0 147 22 1000 127 0 1296 254 0 0 0 0 0 0 00 0 0 1000 0 0 1000 256 0 0 0 0 0 0 0 0 0 0 0 0 6 6 260 0 0 0 0 0 0 0 00 0 0 127 0 127 262 0 0 0 0 0 0 0 0 147 0 0 0 0 147 264 0 0 0 0 0 0 0 00 0 0 0 0 0 266 0 0 0 564 0 0 0 0 0 0 0 0 0 564 268 0 0 0 0 0 0 0 0 0 00 0 553 553 274 0 0 0 0 0 0 0 0 0 0 0 0 0 0 278 0 0 0 53 0 0 0 0 0 0 0 0113 167

Turning now to FIG. 3, Ethane to VCM Oxydehydro-chlorination WithCis/Trans Recycle Process 300 modifies Ethane to VCMOxydehydro-chlorination Process 200 with DCE (dichloroethylene)Hydrogenation Unit 280 for (a) hydrogenating cis-1,2-dichloroethyleneand trans-1,2-dichloroethylene from Cis/trans-1,2-dichloroethyleneStream 260 and (b) recycling the output stream to Reactor 202. In analternative embodiment, Streams 230, 260, and 262 are separated as onesingle blended stream in Heavies Column 220 and the single blendedstream is recycled to DCE Hydrogenation Unit 280.

Table 2 presents further detail in components identified in the Figures.

TABLE 2 Component detail Draw- ing Element Name Description 102 ReactorFluid bed ethane reactor. Vertically oriented reactor system with gasfeed at bottom and outlet at top. Vertical cooling tubes in bed andinternal cyclones (up to 3 in series) located at the top. Typicaldiameters up to 20 feet. Height of fluid bed 30 to 50 feet, with totalheight of 80 feet. The reactor temperature of >400° C. requires that ahigh nickel alloy be used for construction. 104 RCL Hydrogenationreactor for converting the Hydro- unsaturated compounds (most arechlorinated, such genation as cis-1,2 dichloroethylene or trans-1,2dichloroethylene) to their saturated derivatives for recycle to thereactor. 106 Cool and Product gas from the reactor is cooled and theScrub condensate separated from the vapor. The condensate has both aconcentrated HCl aqueous phase and an organic phase. 108 Phase Gravityseparation of the aqueous and organic Separate phases from Cooler 106 ispreferably achieved with a horizontal tank provided with internalbaffles to allow the heavy phase (most likely the aqueous/acid phase,but the nature of the phases depend on the exact composition of organicsin the phases) to be removed from one end of the vessel. The lighterphase flows over the baffle into the second half of the vessel forremoval. The aqueous phase is then, in some embodiments, stripped oforganics. 110 HCl The aqueous HCl stream from the separator is Recoveryrecovered as anhydrous HCl for recycle to the reactor usingtraditionally deployed approaches which are apparent to those of skill.112 Direct Reactor for the chlorination of ethylene. This is Chlor-typically accomplished by injecting the chlorine ination and ethyleneinto the bottom of a vessel containing EDC. The reactants form EDC; thenet product removed as an overhead vapor. The heat of reaction providesthe driving force for the vaporization. 114 Product Separation column,with refrigerated condensers at Split the top to allow separation of thelights for recycle from the chlorinated organics. 116 EDC Standarddistillation columns for the purification of Recovery EDC. 118 Vent Venttreatment is achieved with an incinerator for Treatment the oxidation oforganics (including chlorinated (TOX) organics) to water vapor, carbondioxide, and hydrogen chloride. The vent gas is scrubbed with water torecover HCl as a relatively dilute (10 to 20% HCl stream) for otheruses. This unit is typical of those found throughout the chemicalindustry and should be apparent to those of skill. 120 Drying Prior tothe final separation of the VCM from the other products, water isremoved in a drying column. The pressure and temperature are adjustedsuch that the water is removed from the bottom of the column and the dryproduct is removed from the top. 122 VCM Final purification of the VCMproduct as practiced Columns in industry. 124 Recycle A distillationcolumn to effect the separation of the Products cis and trans 1,2dichloroethylenes and EDC from Column the heavier (higher molecularweight) components. The recovered components are sent to thehydrogenation reactor prior to recycling to the reactor. 202 ReactorEthylene/ethane oxydehydro-chlorination reactor. A fluid bed version(preferred) of the reactor is a vertically oriented reactor system withgas feed at bottom and with the outlet at the top. Vertical coolingtubes are positioned in the bed, and internal cyclones (up to 3 inseries) are located at the top. Typical diameter of the reactor is lessthan 20 feet. Height of fluid bed is between 30 feet and 50 feet, with atotal height of 80 feet for the reactor. The fixed bed version of thereactor is a vertical exchanger type catalytic reactor with tubes from 1to 1.5 inches diameter. The reactor temperature of >400° C. requiresthat a high nickel alloy be used for construction. 204 Cool and Effluentgas from the reactor is cooled with a Condense graphite block orgraphite tube heat exchanger. The condensate has both a concentrated HClaqueous phase and an organic phase. 206 Phase Gravity separation of theaqueous and organic Separate phases from Step 204 is preferably achievedwith a horizontal tank provided with internal baffles to allow the heavyphase (most likely the aqueous/acid phase, but the nature of the phasesdepend on the exact composition of organics in the phases) to be removedfrom one end of the vessel. The lighter phase flows over the baffle intothe second half of the vessel for removal. The aqueous phase is then, insome embodiments, stripped of organics. 208 HCl The aqueous HCl streamfrom the separator is Recovery recovered as anhydrous HCl for recycle tothe reactor using traditionally deployed approaches which are apparentto those of skill. 210 Product A separation column, with refrigeratedcondensers Split at the top to allow separation of the lights forrecycle from the chlorinated organics, is preferably used for thissplitting operation. 212 C2 Ab- Recovery of ethane and ethylene in thepurge sorption stream is achieved by absorption into a and hydrocarbonor other absorbing liquid in an Stripper absorber, with a strippingoperation in a second column. The recovered hydrocarbons are thenrecycled “back” to the main recycle stream and further to the reactor.214 Vent Vent treatment is achieved with an incinerator for Treatmentthe oxidation of organics (including chlorinated (TOX) organics) towater vapor, carbon dioxide, and hydrogen chloride. The vent gas isscrubbed with water to recover HCl as a relatively dilute (10 to 20% HClstream) for other uses. This unit is typical of those found throughoutthe chemical industry and should be apparent to those of skill. 216Drying Prior to the final separation of the VCM from the other productsin the raw product stream after lights have been stripped, water isremoved in a drying column. The pressure and temperature are preferablyadjusted such that the water is removed from the bottom of the columnand the dry product is removed from the top. 218 VCM VCM is purified bymethods as practiced in Columns industry and apparent to those of skill.220 Heavies Heavies are separated using a distillation column Columneffecting the separation of (a) the cis and trans 1,2 dichloroethylenesand (b) EDC from heavier (higher molecular weight) components. 276 HClAb- HCl absorption is achieved with a scrubber column sorption removingHCl from the gas stream into an aqueous solution. 280 Hydro-Hydrogenation is achieved in a reactor for genation converting theunsaturated compounds (most being chlorinated, such as cis or trans 1,2dichloroethylenes) to their saturated derivatives for recycle to thereactor.

EXAMPLES

Specifics in catalysts are further clarified by a consideration of thefollowing examples, which are intended to be purely exemplary.

Example 1

To demonstrate the production of vinyl chloride from a stream comprisingethylene, a porous, refractory composition comprising lanthanum wasprepared. A solution of LaCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (obtainedfrom J.T. Baker Chemical Company) in 8 parts of deionized water.Dropwise addition with stirring of ammonium hydroxide (obtained fromFisher Scientific, certified ACS specification) to neutral pH (byuniversal test paper) caused the formation of a gel. The mixture wascentrifuged, and the solution decanted away from the solid.Approximately 150 ml of deionized water was added and the gel wasstirred vigorously to disperse the solid. The resulting solution wascentrifuged and the solution decanted away. This washing step wasrepeated two additional times. The collected, washed gel was dried fortwo hours at 120 degrees Celsius and subsequently calcined at 550 deg.C. for four hours in air. The resulting solid was crushed and sieved toyield particles suitable for additional testing. This procedure produceda solid matching the X-ray powder diffraction pattern of LaOCl.

The particles were placed in a pure nickel (alloy 200) reactor. Thereactor was configured such that ethylene, ethane, HCl, O₂ and inert gas(He and Ar mixture) could be fed to the reactor. The function of theargon was as an internal standard for the analysis of the reactor feedand effluent by gas chromatography. Space time is calculated as thevolume of catalyst divided by the flow rate at standard conditions. Feedrates are molar ratios. The reactor system was immediately fed anethane-containing stream with the stoichiometry of one ethane, one HCland one oxygen. This provides balanced stoichiometry for the productionof VCM from ethylene.

Table 3 below sets forth the results of reactor testing using thiscomposition.

Column 1 of Table 3 shows the high selectivity to vinyl chloride whenthe catalyst system is fed ethylene under oxidizing conditions in thepresence of HCl. The composition contains helium in order to mimic areactor operated with air as the oxidant gas.

Column 2 of Table 3 shows the high selectivity to vinyl chloride whenthe catalyst system is fed ethylene under oxidizing conditions in thepresence of HCl. The composition is now fuel rich to avoid limitationsimposed by flammability and contains no helium.

Column 3 of Table 3 shows the high selectivity to vinyl chloride andethylene when the catalyst system is fed ethane under oxidizingconditions in the presence of HCl. The composition mimics a reactoroperated with air as the oxidant gas. There is no ethylene present inthe feed. The ethylene present in the reactor is the product of thepartial oxidation of ethane.

Column 4 of Table 3 shows the result when both ethane and ethylene arefed. The reactor is operated in such a way as to insure that the amountof ethylene entering the reactor and exiting the reactor are equal.Operated in this fashion, the ethylene gives the appearance of an inertdiluent, and only ethane is being converted. The results show a highyield of vinyl chloride and 1,2-dichloroethane. Argon is used as aninternal standard to insure that the ethylene flux entering the reactorand the ethylene flux exiting the reactor are equal. The ratio of theethylene to argon integrated chromatographic peak is identical for thereactor feed and product stream. In this way the recycle of ethylene issimulated within the reactor device.

TABLE 3 Feed Mole Ratios C₂H₄ 2 3.7 0 3 C₂H₆ 0 0 1 2 HCl 2 2 1 2.5 O₂ 11 1 1 Inerts 6.8 0 4 0 T (deg. C.) 401 400 401 419 Space time (s) 12.35.0 21.8 12.4 O₂ conv. (pct) 47.3 53.7 54.8 93.9 Selectivities (Percent)C₂H₄ — — 44.7 — C₂H₄Cl₂ 10.7 14.0 0.1 12.8 VCM 76.6 78.1 34.5 68.5

Example 2

To further demonstrate the utility of the composition, ethylene isoxidatively converted to vinyl chloride using a variety of chlorinesources. A solution of LaCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Avocado Research Chemicals Ltd.) in 6.6 parts of deionized water.Rapid addition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was filtered to collect the solid. Thecollected gel was dried at 120 deg C. prior to calcination at 550 deg C.for four hours in air. The resulting solid was crushed and sieved. Thesieved particles were placed in a pure nickel (alloy 200) reactor. Thereactor was configured such that ethylene, HCL, oxygen,1,2-dichloroethane, carbon tetrachloride and helium could be fed to thereactor. Space time is calculated as the volume of catalyst divided bythe flow rate at standard temperature and pressure. Feed rates are molarratios. The composition was heated to 400 deg C. and treated with a1:1:3 HCl:O₂:He mixture for 2 hours prior to the start of operation.

The composition formed was operated to produce vinyl chloride by feedingethylene, a chlorine source and oxygen at 400 deg C. The following tableshows data obtained between 82 and 163 hours on stream using differentchlorine sources. Chlorine is supplied as HCl, carbon tetrachloride and1,2-dichloroethane. VCM signifies vinyl chloride. Space time iscalculated as the volume of catalyst divided by the flow rate atstandard temperature and pressure. The reactors are operated with thereactor exit at ambient pressure. Both ethylene and 1,2-dichloroethaneare termed to be C₂ species.

TABLE 4 Feed mole ratios C₂H₄ 2.0 2.0 2.0 2.0 C₂H₆ 0.0 0.0 0.0 0.0 CCl₄0.5 0.5 0.0 0.0 C₂H₄Cl₂ 0.0 0.0 1.8 0.0 HCl 0.0 0.0 0.0 1.9 O₂ 1.0 1.01.0 1.0 He + Ar 8.9 9.0 8.9 6.7 T (deg C.) 400 399 401 400 Space time(s) 8.0 4.0 8.6 4.9 Fractional conversions (Percent) C₂H₄ 40.4 27.0 18.720.1 C₂H₆ 0.0 0.0 0.0 0.0 CCl₄ 94.8 78.4 0.0 0.0 C₂H₄Cl₂ 0.0 0.0 98.30.0 HCl 0.0 0.0 0.0 44.7 O₂ 68.8 42.0 55.2 37.8 Selectivities based onmoles of C₂ converted VCM 59.6 56.4 86.0 78.5 C₂H₄Cl₂ 14.8 30.7 0.0 2.2C₂H₅Cl 0.6 0.4 0.2 1.6

These data show that a variety of chlorine sources can be used in theoxidative production of vinyl. The use of carbon tetrachloride,1,2-dichloroethane and HCl all produce vinyl chloride as the dominantproduct.

Example 3

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromAvocado Research Chemicals Ltd.) in 6.67 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel and yielded a final pH of 8.85. The mixture wasfiltered to collect the solid. The collected material was calcined inair at 550 deg C. for four hours. The resulting solid was crushed andsieved. The sieved particles were placed in a pure nickel (alloy 200)reactor. The reactor was configured such that ethylene, ethane, HCl,oxygen, and inert (helium and argon mixture) could be fed to thereactor.

Table 5 shows data wherein the reactor feeds were adjusted such that theflux of ethylene (moles/minute) entering the reactor and the flux ofethylene exiting the reactor were substantially equal. Reactor feedswere similarly adjusted such that the fluxes of HCl entering and exitingthe reactor were substantially equal. Oxygen conversion was set atslightly less than complete conversion to enable the monitoring ofcatalyst activity. Operated in this manner, the consumed feeds areethane, oxygen, and chlorine. Both ethylene and HCl give the appearanceof neither being created nor consumed. Space time is calculated as thevolume of catalyst divided by the flow rate at standard temperature andpressure. The example further illustrates the use of chlorine gas as achlorine source in the production of vinyl chloride.

TABLE 5 Feed mole ratios C₂H₄ 2.1 C₂H₆ 4.5 Cl₂ 0.5 HCl 2.4 O₂ 1.0 He +Ar 7.4 T (° C.) 400 Space time (s) 9.4 Fractional conversions (Pct.)C₂H₄ 1.8 C₂H₆ 27.3 Cl₂ 99.8 HCl −1.4 O₂ 96.4 Selectivities (Pct) VCM79.0 C₂H₄Cl₂ 7.2 C₂H₅Cl 1.7 CO_(x) 5.1 C₂H₄ 0.5

In common with all examples herein, VCM signifies vinyl chloride.C₂H₄Cl₂ is solely 1,2-dichloroethane. COX is the combination of CO andCO₂.

Example 4 through Example 11

Example 4 through Example 11 illustrate the preparation of numerous rareearth compositions, each containing only one rare earth material. Dataillustrating the performance of these compositions are set forth inTable 6.

Example 4

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromAldrich Chemical Company) in 6.67 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was centrifuged to collect the solid.Solution was decanted away from the gel and discarded. The gel wasresuspended in 6.66 parts of deionized water. Centrifuging allowedcollection of the gel. The collected gel was dried at 120 deg C. priorto calcination at 550 deg C. for four hours in air. The resulting solidwas crushed and sieved. The sieved particles were placed in a purenickel (alloy 200) reactor. The reactor was configured such thatethylene, ethane, HCl, oxygen, and inert (helium and argon mixture)could be fed to the reactor. Powder x-ray diffraction shows the materialto be LaOCl. The BET surface area is measured to be 42.06 m²/g. Thespecific performance data for this example are set forth below in Table6.

Example 5

A solution of NdCl₃ in water was prepared by dissolving one part ofcommercially available hydrated neodymium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. Powder x-ray diffraction shows the material to be NdOCl.The BET surface area is measured to be 22.71 m²/g. The specificperformance data for this example are set forth below in Table 6.

Example 6

A solution of PrCl₃ in water was prepared by dissolving one part ofcommercially available hydrated praseodymium chloride (Alfa Aesar) in6.67 parts of deionized water. Rapid addition with stirring of 6 Mammonium hydroxide in water (diluted certified ACS reagent, obtainedfrom Fisher Scientific) caused the formation of a gel. The mixture wasfiltered to collect the solid. The collected gel was dried at 120 deg C.prior to calcination in air at 550 deg C. for four hours. The resultingsolid was crushed and sieved. The sieved particles were placed in a purenickel (alloy 200) reactor. The reactor was configured such thatethylene, ethane, HCl, oxygen, and inert (helium and argon mixture)could be fed to the reactor. Powder x-ray diffraction shows the materialto be PrOCl. The BET surface area is measured to be 21.37 m²/g. Thespecific performance data for this example are set forth below in Table6.

Example 7

A solution of SmCl₃ in water was prepared by dissolving one part ofcommercially available hydrated samarium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination at 500 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCL oxygen, and inert (helium and argon mixture) could be fed tothe reactor. Powder x-ray diffraction shows the material to be SmOCl.The BET surface area is measured to be 30.09 m²/g. The specificperformance data for this example are set forth below in Table 6.

Example 8

A solution of HoCl₃ in water was prepared by dissolving one part ofcommercially available hydrated holmium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination at 500 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 20.92 m²/g. Thespecific performance data for this example are set forth below in Table6.

Example 9

A solution of ErCl₃ in water was prepared by dissolving one part ofcommercially available hydrated erbium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination at 500 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCL oxygen, and inert (helium and argon mixture) could be fed tothe reactor. The BET surface area is measured to be 19.80 m²/g. Thespecific performance data for this example are set forth below in Table6.

Example 10

A solution of YbCl₃ in water was prepared by dissolving one part ofcommercially available hydrated ytterbium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination at 500 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 2.23 m²/g. Thespecific performance data for this example are set forth below in Table6.

Example 11

A solution of YCl₃ in water was prepared by dissolving one part ofcommercially available hydrated yttrium chloride (Alfa Aesar) in 6.67parts of deionized water. Rapid addition with stirring of 6 M ammoniumhydroxide in water (diluted certified ACS reagent, obtained from FisherScientific) caused the formation of a gel. The mixture was filtered tocollect the solid. The collected gel was dried at 120 deg C. prior tocalcination at 500 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 29.72 m²/g. Thespecific performance data for this example are set forth below in Table6.

TABLE 6 Rare Earth Oxychloride Compositions Operated to Produce VinylChloride Example 5 6 7 8 9 10 11 12 Feed mole ratios C₂H₄ 3.6 4.2 3.73.6 3.6 3.6 4.2 3.6 HCl 2.0 2.3 2.0 2.0 2.0 2.0 2.3 2.0 O₂ 1.0 1.0 1.01.0 1.0 1.0 1.0 1.0 He + Ar 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 T (deg C.)399 403 401 400 400 400 400 399 Space time (s) 8.7 21.3 11.4 17.6 17.722.8 23.1 21.3 Fractional conversions (Percent) C₂H₄ 23.7 13.2 22.8 14.712.7 15.4 3.3 13.8 HCl 47.6 24.9 40.9 20.8 15.9 22.4 5.0 19.8 O₂ 58.859.4 55.0 53.4 48.1 48.8 21.2 47.8 Selectivities (Percent) VCM 75.3 74.474.2 61.0 33.3 44.0 6.1 35.0 C₂H₄Cl₂ 11.3 2.9 6.1 2.9 14.5 17.5 8.8 18.8C₂H₅Cl 3.5 6.9 4.4 10.6 16.8 12.8 37.0 16.5 CO_(x) 4.8 11.8 9.7 22.433.8 23.1 26.4 27.5

These data show the utility of bulk rare earth containing compositionsfor the conversion of ethylene containing streams to vinyl chloride.

Example 12 through Example 16

Example 12 through Example 16 illustrate the preparation of numerousrare earth compositions, each containing a mixture of rare earthmaterials. Data illustrating the performance of these data are set forthin Table 7.

Example 12

A solution of LaCl₃ and NdCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Spectrum Quality Products) and 0.67 parts of commercially availablehydrated neodymium chloride (Alfa Aesar) in 13.33 parts of deionizedwater. Rapid addition with stirring of 6 M ammonium hydroxide in water(diluted certified ACS reagent, obtained from Fisher Scientific) causedthe formation of a gel. The final pH was measured as 8.96. The mixturewas centrifuged to collect the solid. Solution was decanted away fromthe gel and discarded. The collected gel was dried at 80 deg C. prior tocalcination in air at 550 deg. C for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 21.40 m²/g. Thespecific performance data for this example are set forth below in Table7.

Example 13

A solution of LaCl₃ and SmCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Spectrum Quality Products) and 0.67 parts of commercially availablehydrated samarium chloride (Alfa Aesar) in 13.33 parts of deionizedwater. Rapid addition with stirring of 6 M ammonium hydroxide in water(diluted certified ACS reagent, obtained from Fisher Scientific) causedthe formation of a gel. The final pH was measured as 8.96. The mixturewas centrifuged to collect the solid. Solution was decanted away fromthe gel and discarded. The collected gel was dried at 80 deg C. prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 21.01 m²/g. Thespecific performance data for this example are set forth below in Table7.

Example 14

A solution of LaCl₃ and YCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Spectrum Quality Products) and 0.52 parts of commercially availablehydrated yttrium chloride (Alfa Aesar) in 13.33 parts of deionizedwater. Rapid addition with stirring of 6 M ammonium hydroxide in water(diluted certified ACS reagent, obtained from Fisher Scientific) causedthe formation of a gel. The final pH was measured as 8.96. The mixturewas centrifuged to collect the solid. Solution was decanted away fromthe gel and discarded. The collected gel was dried at 80 deg C. prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert helium and argon mixture) could be fed tothe reactor. The BET surface area is measured to be 20.98 m²/g. Thespecific performance data for this example are set forth below in Table7.

Example 15

A solution of LaCl₃ and HoCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Spectrum Quality Products) and one part of commercially availablehydrated holmium chloride (Alfa Aesar) in 13.33 parts of deionizedwater. Rapid addition with stirring of 6 M ammonium hydroxide in water(diluted certified ACS reagent, obtained from Fisher Scientific) causedthe formation of a gel. The final pH was measured as 8.64. The mixturewas centrifuged to collect the solid. Solution was decanted away fromthe gel and discarded. The collected gel was dried at 80 deg C. prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 19.68 m²/g. Thespecific performance data for this example are set forth below in Table7.

Example 16

A solution of LaCl₃ and HoCl₃ in water was prepared by dissolving onepart of commercially available hydrated lanthanum chloride (purchasedfrom Spectrum Quality Products) and 0.75 parts of commercially availablehydrated ytterbium chloride (Alfa Aesar) in 13.33 parts of deionizedwater. Rapid addition with stirring of 6 M ammonium hydroxide in water(diluted certified ACS reagent, obtained from Fisher Scientific) causedthe formation of a gel. The final pH was measured as 9.10. The mixturewas centrifuged to collect the solid. Solution was decanted away fromthe gel and discarded. The collected gel was dried at 80 deg C. prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 20.98 m²/g. Thespecific performance data for this example are set forth below in Table7.

TABLE 7 Performance of Compositions Containing Two Rare earth materialsExample 13 14 15 16 17 Feed mole ratios C₂H₄ 3.7 3.6 3.6 3.6 3.6 HCl 2.02.0 2.0 2.0 2.0 O₂ 1.0 1.0 1.0 1.0 1.0 He + Ar 0.2 0.2 0.2 0.2 0.2 T (°C.) 401 401 400 399 400 Space time (s) 3.7 15.7 13.7 16.9 20.6Fractional conversions (Percent) C₂H₄ 16.8% 11.3 12.5 12.4 9.2 HCl 36.013.1 18.1 11.9 15.9 O₂ 45.9 47.2 52.2 47.1 38.7 Selectivities (Percent)VCM 75.8 51.0 51.4 28.9 11.1 C₂H₄Cl₂ 9.7 7.5 12.4 14.5 20.6 C₂H₅Cl 4.111.8 8.9 17.0 23.8 CO_(x) 6.9 27.5 25.8 38.9 43.8

These data further show the utility of bulk rare earth containingcompositions containing mixtures of the rare earth materials for theconversion of ethylene containing streams to vinyl chloride.

Example 17 through Example 24

Example 17 through Example 24 are compositions containing rare earthmaterials with other additives present.

Example 17

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromAldrich Chemical Company) in 6.67 parts of deionized water. 0.48 partsof ammonium hydroxide (Fisher Scientific) was added to 0.35 parts ofcommercially prepared CeO₂ powder (Rhone-Poulenc). The lanthanum andcerium containing mixtures were added together with stirring to form agel. The resulting gel containing mixture was filtered and the collectedsolid was calcined in air at 550 deg C. for 4 hours. The resulting solidwas crushed and sieved. The sieved particles were placed in a purenickel (alloy 200) reactor. The reactor was configured such thatethylene, ethane, HCl, oxygen, and inert (helium and argon mixture)could be fed to the reactor. The specific performance data for thisexample are set forth below in Table 8.

Example 18

A lanthanum containing composition prepared using the method of Example5 was ground with a mortar and pestle to form a fine powder. One part ofthe ground powder was combined with 0.43 parts BaCl₂ powder and furtherground using a mortar and pestle to form an intimate mixture. Thelanthanum and barium containing mixture was pressed to form chunks. Thechunks were calcined at 800 deg C. in air for 4 hours. The resultingmaterial was placed in a pure nickel (alloy 200) reactor. The reactorwas configured such that ethylene, ethane, HCl, oxygen, and inert(helium and argon mixture) could be fed to the reactor. The specificperformance data for this example are set forth below in Table 8.

Example 19

Dried Grace Davison Grade 57 silica was dried at 120 deg C. for 2 hours.A saturated solution of LaCl₃ in water was formed using commerciallyavailable hydrated lanthanum chloride. The dried silica was impregnatedto the point of incipient wetness with the LaCl₃ solution. Theimpregnated silica was allowed to air dry for 2 days at ambienttemperature. It was further dried at 120 deg C. for 1 hour. Theresulting material was placed in a pure nickel (alloy 200) reactor. Thereactor was configured such that ethylene, ethane, HCl, oxygen, andinert (helium and argon mixture) could be fed to the reactor. Thespecific performance data for this example are set forth below in Table8.

Example 20

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromSpectrum Quality Products) in 6.67 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was centrifuged to collect the solid.Solution was decanted away from the gel and discarded. The gel wasresuspended in 12.5 parts of acetone (Fisher Scientific), centrifuged,and the liquid decanted away and discarded. The acetone washing step wasrepeated 4 additional times using 8.3 parts acetone. The gel wasresuspended in 12.5 parts acetone and 1.15 parts of hexamethyldisilizane(purchased from Aldrich Chemical Company) was added and the solution wasstirred for one hour. The mixture was centrifuged to collect the gel.The collected gel was allowed to air dry at ambient temperature prior tocalcination in air at 550 deg C. for four hours. The resulting solid wascrushed and sieved. The sieved particles were placed in a pure nickel(alloy 200) reactor. The reactor was configured such that ethylene,ethane, HCl, oxygen, and inert (helium and argon mixture) could be fedto the reactor. The BET surface area is measured to be 58.82 m²/g. Thespecific performance data for this example are set forth below in Table8.

Example 21

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (Alfa Aesar) and0.043 parts of commercially available HfCl₄ (purchased from AcrosOrganics) in 10 parts of deionized water. Rapid addition with stirringof 6 M ammonium hydroxide in water (diluted certified ACS reagent,obtained from Fisher Scientific) caused the formation of a gel. Themixture was centrifuged to collect the solid. Solution was decanted awayfrom the gel and discarded. The collected gel was dried at 80 deg C.overnight prior to calcination at 550 deg C. for 4 hours. The specificperformance data for this example are set forth below in Table 8.

Example 22

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (Alfa Aesar) and0.086 parts of commercially available HfCl₄ (purchased from AcrosOrganics) in 10 parts of deionized water. Rapid addition with stirringof 6 M ammonium hydroxide in water (diluted certified ACS reagent,obtained from Fisher Scientific) caused the formation of a gel. Themixture was centrifuged to collect the solid. Solution was decanted awayfrom the gel and discarded The collected gel was dried at 80 deg C.overnight prior to calcination at 550 deg C. for 4 hours. The specificperformance data for this example are set forth below in Table 8.

Example 23

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (Alfa Aesar) and0.043 parts of commercially available ZrOCl₂ (purchased from AcrosOrganics) in 10 parts of deionized water. Rapid addition with stirringof 6 M ammonium hydroxide in water (diluted certified ACS reagent,obtained from Fisher Scientific) caused the formation of a gel. Themixture was centrifuged to collect the solid. Solution was decanted awayfrom the gel and discarded. The gel was resuspended in 6.67 partsdeionized water and subsequently centrifuged. The solution was decantedaway and discarded. The collected gel was calcined at 550 deg C. for 4hours. The specific performance data for this example are set forthbelow in Table 8.

Example 24

A solution of LaCl₃ in water was prepared by dissolving commerciallyavailable hydrated lanthanum chloride in deionized water to yield a 2.16M solution. Commercially produced zirconium oxide (obtained fromEngelhard) was dried at 350 deg C. overnight. One part of the zirconiumoxide was impregnated with 0.4 parts of the LaCl₃ solution. The samplewas dried in air at room temperature and then calcined in air at 550 degC. for 4 hours. The resulting solid was crushed and sieved. The sievedparticles were placed in a pure nickel (alloy 200) reactor. The reactorwas configured such that ethylene, ethane, HCL oxygen, and inert (heliumand argon mixture) could be fed to the reactor. The specific performancedata for this example are set forth below in Table 8.

TABLE 8 Rare Earth Compositions with Additional Components Example 18 1920 21 22 23 24 25 Feed mole ratios C₂H₄ 3.7 3.6 3.7 3.7 3.7 3.7 3.6 3.7HCl 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 O₂ 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0He + Ar 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 T (° C.) 400 401 400 399 401 400400 401 Space time (s) 4.8 20.3 6.7 3.6 7.9 7.8 12.8 16.7 Fractionalconversions (Percent) C₂H₄ 18.2 11.7 14.1 24.6 18.5 16.5 18.7 15.2 HCl34.6 22.1 24.4 57.1 40.9 38.2 35.2 21.1 O₂ 55.6 33.2 48.0 52.0 50.3 47.450.9 56.4 Selectivities (Percent) VCM 64.5 54.6 53.6 56.0 76.4 71.8 73.255.1 C₂H₄Cl₂ 11.5 15.2 10.0 31.4 9.6 12.7 5.2 7.3 C₂H₅Cl 5.0 10.0 7.42.9 4.0 4.9 4.9 12.4 CO_(x) 10.8 18.6 26.6 6.0 7.6 8.8 13.6 24.1

These data show the production of vinyl chloride from ethylenecontaining streams using lanthanum-based catalysts that contain otherelements or are supported.

Example 25 through Example 30

Example 25 through Example 30 show some of the modifications possible toalter the preparation of useful rare earth compositions.

Example 25

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromSpectrum Quality Products) in 10 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was centrifuged to collect the solid.Solution was decanted away from the gel and discarded. A saturatedsolution of 0.61 parts benzyltriethylammonium chloride (purchased fromAldrich Chemical Company) in deionized water was prepared. The solutionwas added to the gel and stirred. The collected gel was calcined at 550deg C. for 4 hours. The specific performance data for this example areset forth below in Table 9. This example illustrates the use of addedammonium salts to alter the preparation of rare earth compositions.

Example 26

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromSpectrum Quality Products) in 10 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was centrifuged to collect the solid.One part glacial acetic acid was added to the gel and the gelredissolved. Addition of the solution to 26 parts of acetone caused theformation of a precipitate. The solution was decanted away and the solidwas calcined at 550 deg C. for 4 hours. The specific performance datafor this example are set forth below in Table 9. This example shows thepreparation of useful lanthanum compositions by the decomposition ofcarboxylic acid adducts of chlorine containing rare earth compounds.

Example 27

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromSpectrum Quality Products) in 10 parts of deionized water. Rapidaddition with stirring of 6 M ammonium hydroxide in water (dilutedcertified ACS reagent, obtained from Fisher Scientific) caused theformation of a gel. The mixture was centrifuged to collect the solid.The collected gel was resuspended in 3.33 parts of deionized water.Subsequent addition of 0.0311 parts of phosphoric acid reagent(purchased from Fisher Scientific) produced no visible change in thesuspended gel. The mixture was again centrifuged and the solutiondecanted away from the phosphorus containing gel. The collected gel wascalcined for at 550 deg C. for 4 hours. The calcined solid had a BETsurface area of 33.05 m²/g. The specific performance data for thisexample are set forth below in Table 9. This example shows thepreparation of a rare earth composition also containing phosphorus, asphosphate.

Example 28

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased from AcrosOrganics) in 6.66 parts of deionized water. A solution was formed bymixing 0.95 parts of commercially available DABCO, or1,4-diazabicyclo[2.2.2]octane, (purchased from ICN Pharmaceuticals)dissolved in 2.6 parts of deionized water. Rapid mixing with stirring ofthe two solutions caused the formation of a gel. The mixture wascentrifuged to collect the solid. The collected gel was resuspended in6.67 parts of deionized water. The mixture was again centrifuged and thesolution decanted away from the gel. The collected gel was calcined for4 hours at 550 deg C. The calcined solid had a BET surface area of 38.77m²/g. The specific performance data for this example are set forth belowin Table 9. This example shows the utility of an alkyl amine in thepreparation of a useful rare earth composition.

Example 29

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased from AcrosOrganics) in 10 parts of deionized water. To this solution, 2.9 parts ofcommercially available tetramethyl ammonium hydroxide (purchased fromAldrich Chemical Company) was added rapidly and with stirring, causingthe formation of a gel. The mixture was centrifuged and the solutiondecanted away. The collected gel was resuspended in 6.67 parts ofdeionized water. The mixture was again centrifuged and the solutiondecanted away from the gel. The collected gel was calcined for 4 hoursat 550 deg C. The calcined solid had a BET surface area of 80.35 m²/g.The specific performance data for this example are set forth below inTable 9. This example shows the utility of an alkyl ammonium hydroxidefor formation of a useful rare earth composition.

Example 30

A solution of LaCl₃ in water was prepared by dissolving one part ofcommercially available hydrated lanthanum chloride (purchased fromAvocado Research Chemicals Ltd.) in 6.67 parts of deionized water. Tothis solution, 1.63 parts of commercially available 5 N NaOH solution(Fisher Scientific) was added rapidly and with stirring, causing theformation of a gel. The mixture was centrifuged and the solutiondecanted away. The collected gel was calcined for 4 hours at 550 deg C.The calcined solid had a BET surface area of 16.23 m²/g. The specificperformance data for this example are set forth below in Table 9. Thisexample shows the utility of non-nitrogen containing bases for theformation of catalytically interesting materials. Although potentiallyfunctional the tested materials appear to be inferior to those producedusing nitrogen containing bases.

TABLE 9 Additional Preparation Methods for Lanthanum ContainingCompositions Example 26 27 28 29 30 31 Feed mole ratios C₂H₄ 3.6 3.7 3.63.7 3.7 3.7 HCl 2.0 2.0 2.0 2.0 2.0 2.0 O₂ 1.0 1.0 1.0 1.0 1.0 1.0 He +Ar 0.2 0.2 0.2 0.2 0.2 0.2 T (° C.) 401 400 400 399 400 401 Space time(s) 8.6 20.8 4.7 8.7 6.2 20.0 Fractional conversions (Percent) C₂H₄ 18.88.7 15.6 17.4 21.0 9.3 HCl 35.8 7.7 20.0 41.5 48.4 22.3 O₂ 53.0 32.648.8 50.6 56.8 17.9 Selectivities (Percent) VCM 73.4 26.0 72.1 76.8 77.617.5 C₂H₄Cl₂ 8.7 11.9 7.1 7.3 7.8 46.2 C₂H₅Cl 3.5 22.7 5.6 4.2 2.9 25.6CO_(x) 9.8 38.6 12.7 7.6 6.3 9.1

The present invention has been described in an illustrative manner. Inthis regard, it is evident that those skilled in the art, once given thebenefit of the foregoing disclosure, may now make modifications to thespecific embodiments described herein without departing from the spiritof the present invention. Such modifications are to be considered withinthe scope of the present invention which is limited solely by the scopeand spirit of the appended claims.

1. A method of manufacturing vinyl chloride, comprising the steps of:generating a reactor effluent stream by catalytically reacting togetherethane, ethylene, oxygen, and at least one chlorine source of hydrogenchloride, chlorine, or a chlorohydrocarbon, wherein the molar ratio ofsaid ethane to said ethylene is between 0.02 and 50; cooling andcondensing said reactor-effluent stream to provide a raw product streamhaving a first portion of said hydrogen chloride and a raw cooledhydrogen chloride stream having a second portion of said hydrogenchloride; separating said raw product stream into a vinyl chloridemonomer product stream and into a lights stream having said firstportion of said hydrogen chloride; and recycling said lights stream tocatalytically react together with said ethane, said ethylene, saidoxygen, and said chlorine source in said generating step.
 2. The methodof claim 1 wherein said catalytically reacting step uses a catalystcomprising a rare earth material component, with the proviso that thecatalyst is substantially free of iron and copper and with the furtherproviso that when the rare earth material component is cerium thecatalyst further comprises at least one more rare earth materialcomponent other than cerium.
 3. The method of claim 2 wherein the rareearth material component is selected from lanthanum, neodymium,praseodymium, and mixtures thereof.
 4. The method of claim 3 wherein therare earth material component is lanthanum.
 5. The method of claim 1wherein said molar ratio is between 0.1 and
 10. 6. The method of claim 1wherein said molar ratio is between 0.3 and
 4. 7. The method of claim 1wherein one said chlorine source is selected from at least one of achlorinated methane and a chlorinated ethane.
 8. The method of claim 1wherein one said chlorine source is selected from at least one of thechlorinated organic compounds consisting of carbon tetrachloride,1,2-dichloroethane, ethyl chloride, 1,1-dichloroethane, and1,1,2-trichloroethane.
 9. The method of claim 1 wherein1,2-dichloroethane generated in said reacting step is purified for sale.10. The method of claim 1 wherein 1,2-dichloroethane generated in saidreacting step is purified for recycle to said reactor.
 11. The method ofclaim 1 wherein 1,2-dichloroethane generated in said reacting step ispurified for cracking in a vinyl furnace.
 12. A method of manufacturingvinyl chloride, comprising the steps of: generating a reactor effluentstream from a reactor by catalytically reacting together ethane,ethylene, oxygen, and at least one chlorine source of hydrogen chloride,chlorine, or a chlorohydrocarbon, wherein the molar ratio of said ethaneto said ethylene is between 0.02 and 50; cooling and condensing saidreactor effluent stream to provide a raw product stream having a firstportion of said hydrogen chloride and a raw cooled hydrogen chloridestream having a second portion of said hydrogen chloride; separatingsaid raw product stream into a water product stream, a vinyl chloridemonomer product stream, an ethyl chloride stream, acis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended stream,a 1,2-dichloroethane stream, a heavies stream, and a lights streamhaving said first portion of said hydrogen chloride; recovering ananhydrous hydrogen chloride stream from said raw cooled hydrogenchloride stream; recycling said anhydrous hydrogen chloride stream tosaid reactor as said hydrogen chloride reactant; and recycling saidlights stream to said reactor.
 13. The method of claim 12 wherein saidcatalytically reacting step uses a catalyst comprising a rare earthmaterial component, with the proviso that the catalyst is substantiallyfree of iron and copper and with the further proviso that when the rareearth material component is cerium the catalyst further comprises atleast one more rare earth material component other than cerium.
 14. Themethod of claim 13 wherein the rare earth material component is selectedfrom lanthanum, neodymium, praseodymium, and mixtures thereof.
 15. Themethod of claim 14 wherein the rare earth material component islanthanum.
 16. The method of claim 12 wherein said molar ratio isbetween 0.1 and
 10. 17. The method of claim 12 wherein said molar ratiois between 0.3 and
 4. 18. The method of claim 12 wherein one saidchlorine source is selected from at least one of a chlorinated methaneand a chlorinated ethane.
 19. The method of claim 12 wherein one saidchlorine source is selected from at least one of the chlorinated organiccompounds consisting of carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane, and 1,1,2-trichloroethane.
 20. The methodof claim 12 wherein 1,2-dichloroethane generated in said reacting stepis purified for sale.
 21. The method of claim 12 wherein1,2-dichloroethane generated in said reacting step is purified forrecycle to said reactor.
 22. The method of claim 12 wherein1,2-dichloroethane generated in said reacting step is purified forcracking in a vinyl furnace.
 23. A method of manufacturing vinylchloride, comprising the steps of: generating a reactor effluent streamfrom a reactor by catalytically reacting together ethane, ethylene,oxygen, and at least one chlorine source of hydrogen chloride, chlorine,or a chlorohydrocarbon, wherein the molar ratio of said ethane to saidethylene is between 0.02 and 50; cooling and condensing said reactoreffluent stream to provide a raw product stream having a first portionof said hydrogen chloride and a raw cooled hydrogen chloride streamhaving a second portion of said hydrogen chloride; separating said rawproduct stream into a water product stream, a vinyl chloride monomerproduct stream, an ethyl chloride stream, a cis-1,2-dichloroethylene andtrans-1,2-dichloroethylene blended stream, a 1,2-dichloroethane stream,a heavies stream, and a fights stream having said first portion of saidhydrogen chloride; recovering an anhydrous hydrogen chloride stream fromsaid raw cooled hydrogen chloride stream; recycling said anhydroushydrogen chloride stream to said reactor as said hydrogen chloridereactant; dividing said lights stream into a purge stream and a recyclegas stream; absorbing hydrogen chloride from said purge stream toseparate an aqueous hydrogen chloride stream; combining said aqueoushydrogen chloride stream with said raw cooled hydrogen chloride stream;absorbing and recycling to said reactor a C2 stream from said purgestream; and recycling said recycle gas stream to said reactor.
 24. Themethod of claim 23 wherein said catalytically reacting step uses acatalyst comprising a rare earth material component, with the provisothat the catalyst is substantially free of iron and copper and with thefurther proviso that when the rare earth material component is ceriumthe catalyst further comprises at least one more rare earth materialcomponent other than cerium.
 25. The method of claim 24 wherein the rareearth material component is selected from lanthanum, neodymium,praseodymium, and mixtures thereof.
 26. The method of claim 25 whereinthe rare earth material component is lanthanum.
 27. The method of claim23 wherein said molar ratio is between 0.1 and
 10. 28. The method ofclaim 23 wherein said molar ratio is between 0.3 and
 4. 29. The methodof claim 23 wherein one said chlorine source is selected from at leastone of a chlorinated methane and a chlorinated ethane.
 30. The method ofclaim 23 wherein one said chlorine source is selected from at least oneof the chlorinated organic compounds consisting of carbon tetrachloride,1,2-dichloroethane, ethyl chloride, 1,1-dichloroethane, and1,1,2-trichloroethane.
 31. The method of claim 23 wherein1,2-dichloroethane generated in said reacting step is purified for sale.32. The method of claim 23 wherein 1,2-dichloroethane generated in saidreacting step is purified for recycle to said reactor.
 33. The method ofclaim 23 wherein 1,2-dichloroethane generated in said reacting step ispurified for cracking in a vinyl furnace.
 34. A method of manufacturingvinyl chloride, comprising the steps of: generating a reactor effluentstream from a reactor by catalytically reacting together ethane,ethylene, oxygen, and at least one chlorine source of hydrogen chloride,chlorine, or a chlorohydrocarbon, wherein the molar ratio of said ethaneto said ethylene is between 0.02 and 50; cooling and condensing saidreactor effluent stream to provide a raw product stream having a firstportion of said hydrogen chloride and a raw cooled hydrogen chloridestream having a second portion of said hydrogen chloride; separatingsaid raw product steam into a water product stream, a vinyl chloridemonomer product stream, an ethyl chloride stream, acis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended stream,a 1,2-dichloroethane stream, a heavies stream, and a lights streamhaving said first portion of said hydrogen chloride; recovering ananhydrous hydrogen chloride stream from said raw cooled hydrogenchloride stream; recycling said anhydrous hydrogen chloride stream tosaid reactor as said hydrogen chloride reactant; dividing said lightsstream into a purge stream and a recycle gas stream; absorbing hydrogenchloride from said purge stream to separate an aqueous hydrogen chloridestream; combining said aqueous hydrogen chloride stream with said rawcooled hydrogen chloride stream; hydrogenating saidcis-1,2-dichloroethylene and trans-1,2-dichloroethylene blended streamto provide recycle feed to said reactor; absorbing and recycling to saidreactor a C2 stream from said purge stream; and recycling said recyclegas stream to said reactor.
 35. The method of claim 34 wherein saidcatalytically reacting step uses a catalyst comprising a rare earthmaterial component, with the proviso that the catalyst is substantiallyfree of iron and copper and with the further proviso that when the rareearth material component is cerium the catalyst further comprises atleast one more rare earth material component other than cerium.
 36. Themethod of claim 35 wherein the rare earth material component is selectedfrom lanthanum, neodymium, praseodymium, and mixtures thereof.
 37. Themethod of claim 36 wherein the rare earth material component islanthanum.
 38. The method of claim 34 wherein said molar ratio isbetween 0.1 and
 10. 39. The method of claim 34 wherein said molar ratiois between 0.3 and
 4. 40. The method of claim 34 wherein one saidchlorine source is selected from at least one of a chlorinated methaneand a chlorinated ethane.
 41. The method of claim 34 wherein one saidchlorine source is selected from at least one of the chlorinated organiccompounds consisting of carbon tetrachloride, 1,2-dichloroethane, ethylchloride, 1,1-dichloroethane, and 1,1,2-trichloroethane.
 42. The methodof claim 34 wherein 1,2-dichloroethane generated in said reacting stepis purified for sale.
 43. The method of claim 34 wherein1,2-dichloroethane generated in said reacting step is purified forrecycle to said reactor.
 44. The method of claim 34 wherein1,2-dichloroethane generated in said reacting step is purified forcracking in a vinyl furnace.